CN102822731A - Cationic curing liquid crystal sealant and liquid crystal display element - Google Patents

Cationic curing liquid crystal sealant and liquid crystal display element Download PDF

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Publication number
CN102822731A
CN102822731A CN2010800658976A CN201080065897A CN102822731A CN 102822731 A CN102822731 A CN 102822731A CN 2010800658976 A CN2010800658976 A CN 2010800658976A CN 201080065897 A CN201080065897 A CN 201080065897A CN 102822731 A CN102822731 A CN 102822731A
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liquid crystal
polymerization initiators
cationic polymerization
mass parts
sealant
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CN102822731B (en
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小野善之
樱井宏子
武田博之
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Epoxy Resins (AREA)

Abstract

A cation-curable liquid crystal sealant which comprises a cation-polymerizable compound, and a photo cation polymerization initiator and/or a heat cation polymerization initiator, said polymerization initiator(s) being carried on a dispersive microcarrier; and a liquid crystal display element which comprises a pair of substrates facing each other, a sealant provided between said substrates, and liquid crystals enclosed in a sealed area surrounded by said sealant, wherein a cation-curable liquid crystal sealant, which is set forth in any one of claims 1 to 5, is used as the sealant. It is preferred that the cation-curable liquid crystal sealant contains 1-30 mass%, relative to the cation-polymerizable compound, of the photo cation polymerization initiator and/or heat cation polymerization initiator, said polymerization initiator(s) being carried on the dispersive microcarrier.

Description

Cationic curing type liquid crystal sealing agent and liquid crystal display cells
Technical field
The present invention relates to a kind of liquid crystal sealing agent, more particularly, relate to the liquid crystal sealing agent of a kind of light and/or hot cationic curing type.
Background technology
The back substrate that liquid crystal panel (liquid crystal display cells) normally will have thin film transistor (TFT), pixel electrode, alignment films etc. is relative with the front substrate with color filter, electrode, alignment films etc., and the inclosure liquid crystal constitutes between two substrates.And, bonding and used sealant in order to make 2 plate bases.
In recent years, in order to make liquid crystal panel filmization, lightweight or to give that it is flexible, studying the two material of front substrate or preceding back substrate is being replaced with plastics by in the past glass.But the sealant major part of in the past using all is that exploitation is used for glass, is difficult to directly migrate.Use is with the thermosetting resin of epoxy system during as the thermohardening type sealant of major component; Make it 150 ℃ of curing mostly; And when the substrate that the temperature difference of upper and lower base plate or thermal expansivity is different is bonded to each other, then have when panel is cooled to room temperature, liquid crystal panel produces crooked problem.For fear of this situation; Curing catalysts such as organic acid such as inorganic solid acid, salicylic acid such as silicon dioxide have also been attempted in epoxy resin, adding; And under the low temperature below 40 ℃, be cured the method for reaction, but these methods need long-time curing, and therefore impracticable.
On the other hand, be the photo-curable sealant of major component with acrylic ester etc., when solidifying, do not need heat, and can solidify at short notice, so its suitable plastic base.Yet acrylic ester, is peeled off because of simple impact waits a little less than the cementability because cure shrinkage is big sometimes, has problems in therefore actual the use.In addition; Also known have photo-curable composition and heat curing composition are used in combination; And begin to make its semi-solid preparation through photocuring; Carry out completely crued photo-thermal curing type sealant through heating (major part is the heating when utilizing annealing) then, but the sealing agent to the cementability of plastic base still a little less than, existing problems in actual use.
On the other hand; Have and in order to epoxy resin etc. for the photo-curable sealant of 2 yuan of curing systems of light of the light cation-curable of major component and acrylic ester etc. with optical free radical curable (for example; Referring to patent documentation 1), not only when solidifying, do not need heat, can solidify at short notice; And, can significantly improve substrate to organic protection layer and SiO through utilizing the light ring-opening reaction xCementability Deng inorganic protective layer.Yet therefore the acid meeting stripping that produces when ionic light cationic polymerization initiators and cationic curing also has the such problem of voltage retention decline in liquid crystal.
As the manufacturing approach of the liquid crystal panel that uses glass substrate, its main flow is in the vacuum injection mode of using thermal cure sealants, and uses the photocuring heat curing and with the drip method of technology of being called as of type sealant.In the technology of dripping, at first be through point gum machine (dispenser) 2 transparency carriers that have an electrode one on form rectangular seal pattern.Then, whole whole face drips and the coating of liquid crystalline droplet in the transparency carrier frame under the uncured state of sealant, under reduced pressure overlapping again another transparency carrier, and to the sealing irradiation ultraviolet radiation, solidify temporarily.Then, heating makes its formal curing, makes liquid crystal panel.
Use sealant as used liquid crystal panel in this technology of dripping; For example; In patent documentation 2, disclose and a kind ofly made its photocuring, and further made the photo-thermal curing of its heat curing and use the type sealant through contained thermal curing agents through the free radical that irradiation ultraviolet radiation produced.
On the other hand, in patent documentation 3,, a kind of sealant that uses the cationically polymerizable compound has been proposed as the sealant that does not use thermal curing agents.The sealant of this use cationically polymerizable compound is compared with the sealant that uses thermal curing agents, except storage stability well, it is excellent also to have a low temperature rapidly-curable, solidifies the required time to lack, and can shorten advantages such as manufacturing time.
Yet; In the technology of dripping; Because the sealant of its uncured state directly contacts with liquid crystal in its operation, therefore when the sealant of cationically polymerizable compound had been used in employing, cationically polymerizable compound and light cationic polymerization initiators meeting stripping were in liquid crystal; And in the liquid crystal display cells of gained, the orientation that has liquid crystal is chaotic, degradation problem under the voltage retention of liquid crystal display cells.In recent years liquid crystal display cells particularly, because consumer's low power consumption purpose, so it tends to the liquid crystal (low-voltage type liquid crystal) that uses driving voltage low.This low-voltage type liquid crystal particularly because dielectric constant anisotropy is strong, therefore introduce impurity easily, and the orientation of liquid crystal is chaotic, the voltage retention of liquid crystal display cells descends also very remarkable.
In addition; In patent documentation 4; As the light cationic polymerization initiators, a kind of load initiating agent is disclosed, its dispersed minichromosome vector by the photocatalysis ionic salt of supporting also load or metal-organic complex kation and metal or metalloid negative ion Halogen part forms; To the cationically polymerizable compound is insoluble, is used under the situation that does not have non-reactive solvent, carrying out the radioactive ray activate polymerization of cationically polymerizable compound; And proposed to use the light cation-curable composition of this Photoepolymerizationinitiater initiater.
The prior art document
Patent documentation 1: TOHKEMY 2008-96575 communique
Patent documentation 2: TOHKEMY 2001-133794 communique
Patent documentation 3: TOHKEMY 2005-227367 communique
Patent documentation 4: japanese kokai publication sho 61-278507 communique
Summary of the invention
The problem that invention will solve
The problem that the present invention will solve provides a kind ofly has the excellent electrical specification and the cationic curing type liquid crystal sealing agent of cementability, and a kind of liquid crystal display cells that uses this cationic curing type liquid crystal sealing agent and voltage retention excellence is provided.
The method of dealing with problems
The inventor has solved foregoing problems through the cationic polymerization initiators of working load on dispersed minichromosome vector as the cation-curable composition.
As previously mentioned,, therefore when it is blended in the liquid crystal, may reduce the resistance value of liquid crystal, reduce the voltage retention of the liquid crystal display cells of gained because light or hot cationic polymerization initiators are ionic compounds.To this; The inventor finds through cationic polymerization initiators being loaded on the dispersed minichromosome vector; Can reduce stripping significantly, and find can to obtain thus can not to cause that the orientation of liquid crystal is chaotic, the degradation liquid crystal characteristic worsens under the voltage retention of display element liquid crystal sealing agent.
Find in addition,, can obtain the liquid crystal sealing agent that the orientation confusion of liquid crystal, voltage retention decline or electrode corrosion are given birth in a kind of special difficult labour through also using the alkali solid material.
That is, the present invention provides a kind of and contains the cationically polymerizable compound and load on light cationic polymerization initiators and/or the cationic curing type liquid crystal sealing agent of hot cationic polymerization initiators on the dispersed minichromosome vector.
In addition; The present invention provide a kind of have against each other to two substrates, be arranged on the sealant between aforesaid base plate and be sealing into the liquid crystal in the sealing area that aforementioned encapsulant surrounds, and it uses the liquid crystal display cells of aforementioned male ion curing type liquid crystal sealing agent as aforementioned sealant.
The invention effect
The sealant of the application of the invention, even in the technology of dripping, the orientation that also can obtain be difficult to producing liquid crystal is chaotic, the liquid crystal display cells of degradation under the voltage retention of liquid crystal display cells.
Embodiment
(dispersed minichromosome vector)
The cationic polymerization initiators that uses among the present invention loads on the dispersed minichromosome vector.
The dispersed minichromosome vector that uses among the present invention; Be preferably granular; And have full-size and be less than about 50 microns, as far as possible in 0.001～20 micron scope, more preferably 0.01～5 micron, most preferably have a particle diameter of 0.01～2 micron; And be preferably the organic principle that is insoluble to sealant, but promptly in fact measured quantity be insoluble dispersed minute materials.The surface area of this dispersiveness minichromosome vector is big more, and then the amount of the light cationic polymerization initiators of load is many more, and is therefore preferred; But because as a rule, the particle that surface area is big, its particle diameter is little; Operating difficulties; And form agglutination body easily 2 times, hinder the homogeneity of polymerization, so its surface area is preferably 0.1～10000m 2The scope of/g, more preferably 1～5000m 2The scope of/g is preferably 10～2000m again 2/ g further is preferably 30～1500m 2/ g, and most preferably be 30～1200m 2The scope of/g.
Be such silica-based of aerosil, precipitated silica and native silicon dioxide specifically; Zeyssatite; The clay class that bentonitic clay, porcelain earth and attapulgite (attapulgus) are such; Oxide, carbonate and the sulfate of metals such as aluminium, zirconium, titanium, antimony, iron, nickel, zinc, tin, copper, or their potpourri; Such starch, carbon black, graphite, adamas, the polymer class of starch (being cornstarch); The such emulsion class of emulsion of polystyrene, polyvinyl toluene, polyvinyl pyrrolidone, polyacrylic acid, polyacrylate, polymethacrylate etc.; The minute materials of pigment particles or dispersiveness of a size suitable, and can be in its surface or the inner minichromosome vector that contains the light cationic polymerization initiators, cellulose for example in small, broken bits (that is cotton, timber), glass etc.
The alkali solid material of stating after can also using is as dispersed minichromosome vector.But because the alkalescence that the alkali solid material is had can hinder the curing reaction of cationically polymerizable compound, so weak base is more preferably the alkali solid material that the density of the basic group on the perhaps preferred alkaline solid surface is little than highly basic.Suitable when alkaline when having as the alkali solid of carrier, can control the delay curable (character that curing reaction speed is slack-off) of cationically polymerizable compound.
In addition, aforementioned dispersed minichromosome vector preferably sees through employed light, for example ultraviolet ray.
Particularly suitable carrier is an aerosil, for example AEROSIL (Japanese Aerosil Co., Ltd.).As the king-sized preferable alloy oxide of the specific surface area of dispersed minichromosome vector, can enumerate MCM41 such surfactant is carried out mold and synthetic mesopore porous body.In addition, can also enumerate the mesopore porous body that amino acid whose higher order structures such as organic low molecular gel, collagen is carried out the mold made.As the material of mesopore porous body, it is multiple to enumerate silicon dioxide, aluminium oxide, zirconia, titanium dioxide etc.
(cationic polymerization initiators)
As employed cationic polymerization initiators among the present invention; Light cationic polymerization initiators and hot cationic polymerization initiators are arranged, and they are the ionic salt that is made up of metal or metalloid Halogen coordination anion and kation and organic metal coordination kation (below be called ionic salt).Specifically, be organic atom kation of aromatic series and anionic addition product with periodic table VA family, VIA family or VIIA family atom, particularly phosphorus, antimony, bismuth, sulphur, nitrogen and iodine atom of the 15th family, the 16th family and the 17th family's symbol.For example, can enumerate salt such as aromatic series diazo salt, aromatic series salt compounded of iodine, aromatic series sulfonium salt.
(light cationic polymerization initiators)
Employed smooth cationic polymerization initiators among the present invention is the photocatalysis ionic salt that is made up of metal or metalloid Halogen coordination anion and kation and organic metal coordination kation (below be called ionic salt).Specifically, be organic atom kation of aromatic series and anionic addition product with periodic table VA family, VIA family or VIIA family atom, particularly phosphorus, antimony, sulphur, nitrogen and iodine atom of the 15th family, the 16th family and the 17th family's symbol.For example, can enumerate salt such as aromatic series diazo salt, aromatic series salt compounded of iodine, aromatic series sulfonium salt.Give an example carrying out product sold in these salt, can enumerate Optomer SP-150, Optomer SP-151, Optomer SP-170, Optomer SP-171 (all being that Asahi Denka Co., Ltd. makes), UVE-1014 (General Electric Co. Limited's manufacturings), IRGARCURE261 (vapour Ba-Jia Ji manufactured), San-Aid SI-60L, San-Aid SI-80L, UVI-6990 (Union Carbide Corporation's manufacturings), BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (all be greening manufactured), San-Aid SI-100L (all being the manufacturings of three new chemical industry societies), CI-2064, CI-2639, CI-2624, CI-2481 (all be Japanese Cao Da society manufacturing), RHODORSIL PHOTOINITIATOR 2074 (Rhone-poulene manufactured), CD-1012 (Sartomer manufactured) etc.Wherein, Optomer SP-150 is difficult to because of salt causes electrode corrosion, and Optomer SP-170 obtains effective curable easily, and the ionic impurity of RHODORSILPHOTOINITIATOR 2074 is few, so they are more preferably.
The aforementioned lights cationic polymerization initiators can use separately, also can be with also using more than 2 kinds.In addition, can also be as required and with sensitizers such as anthracene system, thioxanthones systems.
In addition; The cooperation ratio of this light cationic polymerization initiators is not special to be limited; And owing to load on the acid that the light cationic polymerization initiators on the dispersed minichromosome vector produces because of rayed; Have than the more difficult tendency to polymerizable compound generation effect of normal conditions, therefore preferably comparing common use amount increases its addition.Specifically, with respect to after cationically photopolymerizable compound 100 mass parts stated, preferably use with the scope of 0.01～20 mass parts.If it is less than 0.01 mass parts; Then the curable of sealant of the present invention may be not enough; And if surpass 20 mass parts; The acid that is then produced by the light cationic polymerization initiators has reached more than the necessary amount that makes the reaction of optical polymerism compound, has therefore improved acid and from sealant, has soaked into the possibility to liquid crystal, and then may make the electrical specification variation of liquid crystal.It is the scope of 0.03～10 mass parts more preferably.
(hot cationic polymerization initiators)
Give an example in the commercially available prod of acidic initiating agent through heat to conduct in the cationic polymerization initiators, can enumerate San-Aid SI60L, San-Aid SI80L, San-Aid SI100L, San-Aid SI110L, San-Aid SI180L (all being that three new chemical industry societies make), CP-66, CP-77 (all being Asahi Denka Co., Ltd.) etc.They also can be used as the light cationic polymerization initiators.In addition, can enumerate CP-66, CP-77 (all being Asahi Denka Co., Ltd.) etc.
The aforementioned hot cationic polymerization initiators can use separately, also can be with also using more than 2 kinds.In addition; The cooperation ratio of this hot cationic polymerization initiators is not special to be limited; And owing to loading on hot cationic polymerization initiators on the dispersed minichromosome vector because the acid that produces of heat; Have than the more difficult tendency to polymerizable compound generation effect of normal conditions, therefore preferably comparing common use amount increases its addition.Specifically, with respect to after cationically polymerizable compound 100 mass parts stated, preferably with 0.01～20 mass parts, 0.03～20 mass parts more preferably, and the scope that further is preferably 0.1～20 mass parts is used.If it is less than 0.01 mass parts; Then the curable of sealant of the present invention may be not enough; And if surpass 20 mass parts; Then reached more than the necessary amount that makes the reaction of cationically polymerizable compound, therefore improved acid and from sealant, soaked into possibility, and then may make the electrical specification variation of liquid crystal to liquid crystal by the acid that hot cationic polymerization initiators produced.It is the scope of 0.03～10 mass parts more preferably.
(carrying method)
Load the dispersed minichromosome vector of cationic polymerization initiators; Can be through metal or metalloid Halogen coordination anion and kation and the cationic ionic salt of organic metal coordination be dissolved in the appropriate solvent; Solvent for example is methylene chloride, methyl alcohol, ethanol, propyl alcohol, acetone, water, nitromethane, toluene, xylene etc. or their mixed solvent, and this solution is mixed with an amount of dispersed carrier material and makes.Desolvate through removing, the light cationic polymerization initiators is loaded in the surperficial or surperficial fine voids of dispersed minichromosome vector.Solvent can be removed through filtration, but might not load on the silicon dioxide effectively and flow out the therefore preferred method that is removed through distillation that adopts owing to being dissolved in ionic salt in the solvent.In addition, when using the light cationic polymerization initiators that decomposes easily,,, and further preferably distilling below 40 ℃ more preferably below 60 ℃ preferably below 100 ℃.
In above-mentioned,, preferably use freeze drying as the drying means of removing the solvent that has dissolved cationic polymerization initiators.Can prevent the aggegation again of dispersed carrier material thus, thereby obtain fine dispersed minichromosome vector.Minichromosome vector is tiny more, then can carry out the curing reaction of cationically polymerizable compound more effectively.Solid after solidifying point like solvent is low, freezing is difficult to distil, and these are difficult under the cryodesiccated situation, also can in solvent, suitably add water, first dry solvent under the freezing temperature of water, and then the remaining chilled water of freeze drying and being removed.
Dispersed minichromosome vector is preferably porous matter, is loaded in the pore of carrier by the cationic polymerization initiators preferred negative of load.This is owing to be adsorbed on the possibility height that the outer cationic polymerization initiators of pore contacts with the resinous principle or the liquid crystal of encapsulant, ionic cationic polymerization initiators stripping, the insulativity of obstruction liquid crystal.Preferably only wash to remove and be adsorbed on the outer cationic polymerization initiators of pore through certain methods.Therefore, for example, the dispersed minichromosome vector that removes the cationic polymerization initiators that unloads through solvent gets final product.As used solvent, preferably cationic polymerization initiators is had minimal dissolubility, can the excessive suitable deliquescent solvent that all dissolves to the cationic polymerization initiators that will be adsorbed in the pore but have dissolving power.It need suitably be selected according to the kind of dispersed carrier material and cationic polymerization initiators.If increase washing times; Though then the outer cationic polymerization initiators of pore is removed, the cationic polymerization initiators amount in the pore also reduces, therefore; Need according in the pore with the amount of the outer residual cationic polymerization initiators of pore, promptly curable and electrical specification decide washing times.
(addition)
If add too much dispersed minichromosome vector, then cationically polymerizable compound thickening may reduce the operating performance such as illustrative of sealant.Therefore, the addition of dispersed minichromosome vector is preferably the scope of the 50 quality % that are no more than the cationically polymerizable compound.Specifically, with respect to cationically polymerizable compound 100 mass parts, use with the scope of 0.1～100 mass parts, be preferably 0.1～50 mass parts, more preferably 1～30 mass parts most preferably is 3～10 mass parts.
On the other hand; As previously mentioned, cationic polymerization initiators preferably uses with the scope of 0.1～20 mass parts with respect to cationically polymerizable compound 100 mass parts; Therefore, preferably use by the retrodict use amount of dispersed minichromosome vector of the amount of the cationically polymerizable initiating agent of load.
On the other hand, according to the surface configuration and the surface area of dispersed minichromosome vector, the most suitable scope of this charge capacity is different.For example; On the little dispersed minichromosome vector of surface area during a large amount of this polymerization initiator of load; This polymerization initiator with multilayer laminated, therefore, is got over away from this polymerization initiator on the outside layer on dispersed minichromosome vector surface on the hollow structure surface of dispersed minichromosome vector; Its absorption affinity more a little less than, this polymerization initiator might dissolve or be dispersed in this polymerizable compound side.This also becomes liquid crystal is polluted and the reason of electrical specification variation, and is therefore not preferred.Further, the big and outwardly open structure according to the peristome that is hollow structure, or bottle-neck type also are different.For example, when the outside opening of peristome of hollow structure, for reason given above can know, to have the sour useful effect that produces by this polymerization initiator in the advantage of this polymerizable compound polymerization though can't carry out a large amount of loads.On the contrary, under the situation of bottle-neck type, even load this a large amount of polymerization initiators, it is also less by the possibility that carrier flows out to this polymerizable compound side, but it exists acidic to some extent diffusing capacity to diminish the possibility that reaction can't effectively be carried out.In detail, though the proterties of dispersed minichromosome vector can exert an influence, as a rule, this polymerization initiator in by the represented charge capacity of the surface area of addition/dispersed minichromosome vector, is preferably 1 * 10 with respect to the charge capacity of dispersed minichromosome vector -7～1g/m 2, more preferably 1 * 10 -6G/m 2～1g/m 2, further be preferably 1 * 10 -6～1 * 10 -2G/m 2, most preferably be 1 * 10 -5～1 * 10 -3G/m 2
The latter is scaled to the average lamination number of this polymerization initiator molecule of per unit area, is estimated as and is equivalent to 1/10 layer～100 layers.
The cationic polymerization initiators of load is identified and is difficult to stripping again.Specifically; With acetone the experimental result that the cationic polymerization initiators of load carries out stripping is again shown; Kind regardless of the dispersed minichromosome vector that uses; Regardless of the charge capacity of the cationic polymerization initiators of load, stripping is in solution (B) again for the cationic polymerization initiators of 30～60 quality %, so its cationic polymerization initiators that has hinted 70～40 quality % is with enough strong adhesion and silica bound.(reference experiment of stating after the reference).The cationically polymerizable compound that uses is lower than the material of acetone as dissolubility, in case therefore infer load cationic polymerization initiators almost no longer stripping in the cationically polymerizable compound, keep steady state (SS).
(particle diameter)
Though the primary particle size of dispersed minichromosome vector is about tens nm, the secondary agglutination body that it produces aggegation mostly and forms hundreds of nm～a few μ m.Attend the catalysis of the cationic polymerization initiators of institute's load in order to give full play to dispersed minichromosome vector, hope to be dispersed to as much as possible the size of primary particle.
(adding method)
Through with load the dispersed minichromosome vector of cationic polymerization initiators add in the cationically polymerizable compound as dispersion medium with the form of powder; And use mixer, screw extruder etc. to stir; Or it is mixing etc. to use three-roller, kneader, double screw extrusion machine etc. to carry out, and can disperse.In order to obtain finer disperse state, the also preferred ball mill etc. that uses.Specifically; Through will load on light cationic polymerization initiators on the dispersed minichromosome vector, after the cationically photopolymerizable compound stated and stir together as the small pearl that stirs particle (medium); Thereby agglutination particle is given impact, sheared ability through stirring particle; Agglutination particle is disperseed, therefore can obtain finer disperse state.
(cationically polymerizable compound)
As the cationically polymerizable compound that uses among the present invention; So long as usually as the known habitual compound with epoxy radicals, oxa-cyclobutyl, vinyl ether group of the polymerizable compound that in the presence of aforementioned cationic polymerization initiators, can carry out cationic polymerization, just not special the qualification.But the compound with oxa-cyclobutyl is because few through amount of hydroxyl groups that polymerization produced, therefore for unfavorable with the cementability of plastics, so preferred a small amount of the use.
As the cationically polymerizable compound that in a part, has 1 above epoxy radicals; For example, can enumerate bisphenol A type epoxy resin (trade name " EPICLON 850CRP ", " EPICLON850S ", " EPICLON 1050 ", " EPICLON 1055 " that DIC society makes), bisphenol f type epoxy resin (trade name " EPICLON 830CRP ", " EPICLON 830 " that DIC society makes), bisphenol-s epoxy resin (trade name " EPICLON EXA1514 " that DIC society makes), A Hydrogenated Bisphenol A type epoxy resin (trade name " EPICLON EXA7015 " that DIC society makes), propylene oxide addition bisphenol A type epoxy resin (trade name " EP-4000S " that rising sun electrification society makes), resorcinol type epoxy resin (trade name " EX-201 " of the long rapids NagaseChemtex manufactured of Japan), biphenyl type epoxy resin (trade name of japan epoxy resin manufactured " EPIKOTE YX-4000H "), dicyclopentadiene-type epoxy resin (trade name " EP-4088S " that rising sun electrification society makes), naphthalene type epoxy resin (trade name " EPICLON HP4032 ", " EPICLON EXA-4700 " that DIC society makes), phenol novolak type epoxy resin (trade name " EPICLON N-770 " that DIC society makes), o-cresol phenolic epoxy varnish (trade name " EPICLON N-670-EXP-S " that DIC society makes), NC-3000P biphenyl phenolic resin varnish type epoxy resins such as (Japanese chemical drug manufactured), ESN-165S naphthol novolacs such as (Dongdu change into manufactured) varnish type epoxy resin, EPIKOTE 630 (japan epoxy resin manufactured), modified rubber type epoxy resin (trade name " PB3600 " that Daicel chemical company makes), bisphenol A-type episulfide resin (trade name of japan epoxy resin manufactured " EPIKOTE YL-7000 ") etc.Can also enumerate alicyclic epoxy resin (trade name " CELLOXIDE 2021 ", " CELLOXIDE 2080 ", " CELLOXIDE 3000 ", " EHPE " that Daicel chemical company makes) etc.
As above-mentioned commercial goods with cationically polymerizable compound of 1 above vinyl ether group; Can enumerate 4-ethyleneoxy butanols (BASF society make trade name " Vinyl-4-hydroxybutylether "), triethylene glycol divinyl ether (trade name " Rapi-Cure DVE-3 " that ISP society makes), 1,4 cyclohexane dimethanol divinyl ether (trade name " CHDVE " that Japanese carbide industrial group makes) etc.
As the cationically polymerizable compound that in a part, has 1 above oxa-cyclobutyl; For example, can enumerate 3-ethyl-3-(phenoxymethyl) oxetanes (trade name " OXT-211 " that East Asia Synesis Company makes), 3-ethyl-3-(cyclohexyl) methyl oxetanes (trade name " CHOX " that East Asia Synesis Company makes) etc.As compound with 2 above oxetanes rings; Can enumerate 1; Two [{ (3-ethyl oxetanes-1-yl) methoxyl } methyl] benzene of 4-(trade name " OXT-121 " that East Asia Synesis Company makes), 1; Two [(3-ethyl oxetanes-3-yl) methoxyl] benzene of 3-(trade name " OXT-223 " that East Asia Synesis Company makes), two [1-ethyl (3-oxa-cyclobutyl)] methyl ether (trade name " OXT-221 " that East Asia Synesis Company makes), phenol phenolic varnish type oxetanes (trade name " PNOX-1009 " that East Asia Synesis Company makes), 4,4 '-two [{ (3-ethyl oxetanes-1-yl) methoxyl } methyl] biphenyl (trade name " OXBP " that emerging product society of space portion makes).
In above-mentioned cationically polymerizable compound,, help bonding viewpoint and consider the polymerizable compound that especially preferably has the epoxy radicals that contains aromatic rings from obtaining cohesive force through utilizing aromatic rings interaction each other.Specifically, can enumerate bisphenol A type epoxy resin (trade name " EPICLON 850CRP ", " EPICLON 850S ", " EPICLON 1050 ", " EPICLON1055 ", " EPICLON 4822 " that DIC society makes), bisphenol f type epoxy resin (trade name " EPICLON830CRP ", " EPICLON 830 " that DIC society makes) etc.Particularly low from viscosity, consider with the also high viewpoint of the dilution effect of the represented compound of general formula (1), be preferably bisphenol A type epoxy resin (trade name " EPICLON 850CRP " that DIC society makes), bisphenol f type epoxy resin (trade name " EPICLON 830CRP " that DIC society makes) especially.
When the encapsulant of using as LCD,, preferably use A Hydrogenated Bisphenol A type epoxy resin from reducing viewpoint consideration to the contaminative of liquid crystal.Specifically, can enumerate the trade name " EX-216L " of (trade name " EPICLON EXA7015 ", the trade name " EPIKOTE YX-8000 " of japan epoxy resin manufactured, " EPIKOTE YX-8034 " that DIC society makes), the long rapids NagaseChemtex manufactured of Japan.
Cationically polymerizable compound of the present invention can also and be used with the composition of radically curing system (below be called radically curing property composition).
(composition of radically curing system)
Radically curing property composition is the composition that comprises free-radical polymerised compound and radical polymerization initiator.As free-radical polymerised compound; So long as the normally used just not special qualification of known habitual compound in UV curing field with (methyl) acryloyl group; And when being used for the liquid crystal panel seal applications, the material that is difficult to mix with liquid crystal can more preferably use.But,, preferably only use the big dipentaerythritol of cure shrinkage five and (methyl) acrylic ester such as six acrylic ester, tetramethylol methane tetraacrylate on a small quantity for fear of excessive cure shrinkage.In addition owing to have carboxylic acid group's free-radical polymerised compound, in preservation may with epoxy reaction, thereby cause composition viscosity sharply to rise, therefore preferably only use on a small quantity.
In backbone structure, has ester bond; And have polyester (methyl) acrylic ester of (methyl) acryloyl group more than at least 2, with epoxy radicals (methyl) acrylic ester of epoxychloropropane modified gained, with (methyl) acrylic ester of modifications such as oxirane, epoxypropane, annular lactone etc., also can preferably use.But, have the acrylic ester of carbamate groups, with the combination of cationic curing system the time,, carbamate groups hinders because of having caused solidifying, therefore preferably only use on a small quantity.
Object lesson as (methyl) acrylic ester that uses among the present invention; For example, can enumerate glycerine monomethacrylates (trade name " BLEMMER GLM " that Japanese grease society makes), acryloxy ethyl phthalic ester (trade name " HOA-MPE " that chemical company of common prosperity society makes), (methyl) benzyl acrylate (trade name of Osaka organic chemistry manufactured " VISCOAT 160 "), Nonylphenoxy polyethylene glycol acrylate (trade name " ARONIX M111 ", " ARONIX M113 ", " ARONIX M117 " that East Asia Synesis Company makes), ECH modification phenoxy group acrylic ester (trade name " ARONIX M5700 " that East Asia Synesis Company makes), EO modification succinic acid acrylic ester (trade name " HOA-MS " that chemical company of common prosperity society makes), EO modified phosphate methacrylate (trade name " P-1M " that chemical company of common prosperity society makes), Abietyl modified epoxy acrylate (trade name that waste river chemical company makes " Bi Sai PVC ー system セ ッ ト) 101 ") wait have (methyl) acrylic ester of 1 (methyl) acryloyl group, (methyl) acrylic ester that two (acryloyl group ethyl) hydroxyethyl isocyanuric acid ester (trade name " ARONIX M215 " that East Asia Synesis Company makes), EO modified bisphenol A diacrylate (trade name " ADPE-150 " that Japanese grease society makes), PO modified bisphenol A diacrylate (trade name " ADBP-200 " that Japanese grease society makes), ECH modified bisphenol A type acrylic ester (trade name " DICLITE UE8200 " that DIC chemical company makes), ECH modification diallyphthalate acid esters (the long rapids trade name " DA-721 " that changes into manufactured), ECH modification hexahydro-phthalic acid diacrylate (the long rapids trade name " DA-722 " that changes into manufactured), tristane dimethanol diacrylate (trade name " IRR214 " that Daicel UCB society Zhi Zaos), Abietyl modified ester acrylic ester (trade name " Bi Sai 115B " that waste river chemical company Zhi Zaos), EO modified phosphate dimethylacrylate (trade name " P-2M " that chemical company of common prosperity society Zhi Zaos), three (acryloxy ethyl) isocyanuric acid ester (trade name " ARONIX M315 " that East Asia Synesis Company makes), dihydroxy methylpropane tetraacrylate (trade name " ARONIX M408 " of East Asia Synesis Company manufacturing), dipentaerythritol acrylate (trade name of Japanese chemical drug manufactured " KAYARAD DPHA "), caprolactone modification dipentaerythritol acrylate (trade name of Japanese chemical drug manufactured " KAYARAD DPCA-30 ", " KAYARAD DPCA-120 ") etc. have (methyl) acryloyl group more than 2 etc.
In above-mentioned free-radical polymerised compound, ester modified (methyl) acrylic ester in particularly using, with Abietyl modified (methyl) acrylic ester, owing to can make solidification compound soft, and help adaptation, therefore preferred especially.Specifically, can enumerate lactone modified hydroxyl pivalic acid neopentylglycol diacrylate (trade name of Japanese chemical drug manufactured " HX620 "), in ester modified BPA epoxy radicals phthalic ester diacrylate (trade name of DAICEL-CYTEC manufactured " EBECRYL3708 "), Abietyl modified epoxy acrylate (trade name " Bi Sai 101 " that waste river chemical company makes) etc.
The use amount of aforementioned free-radical polymerised compound, the scope of the scope of the invention is just not special to be limited so long as do not damage.Specifically, be preferably the scope of 20～70 quality %.
In addition, as the radical photopolymerization initiating agent, for example, can use benzophenone, 2,2-diethoxy acetophenone, benzil, benzoyl isopropyl ether, benzil dimethyl ketal, 1-hydroxycyclohexylphenylketone, thioxanthones etc.These optical free radical polymerization initiators can use separately, also can be with also using more than 2 kinds.
In addition, can also use maleimide compound with light-initiated ability.As the object lesson of maleimide compound, for example can enumerate the maleimide compound of being put down in writing in TOHKEMY 2000-19868 communique, the TOHKEMY 2004-070297 communique with light-initiated ability.
As the free radical thermal polymerization, can enumerate the initiating agent of peroxidating system or azo system.As peroxidating system thermal polymerization, for example, can enumerate 3; 5,5-trimethyl acetyl base superoxide (trade name: PEROYL 355, a day oily society makes), 2; 4-dichloro-benzoyl superoxide (trade name: NYPERCS; Day oily society manufacturing), isobutyl peroxide (trade name: PEROYL IB, day oily society manufacturing), two lauroyl peroxides diacyl peroxides such as (trade names: PEROYL L, day oily society manufacturing); Two (3-methyl-3-methoxyl butyl) peroxy dicarbonate (trade name: PEROYL SOP; Day oily society manufacturing), two-2-methoxyl butyl peroxyization, two carbonic esters (trade name: PEROYL MBP; Day oily society manufacturing), two-2-ethylhexyl peroxy dicarbonate (trade name: PEROYL OPP; Day oily society manufacturing), two-2-ethoxyethyl group peroxy dicarbonate (trade name: PEROYL EEP; Day oily society manufacturing), diisopropyl peroxydicarbonate (trade name: PEROYL IPP; Day oily society manufacturing), two-(4-tert-butylcyclohexyl) peroxy dicarbonate peroxy dicarbonates such as (trade names: PEROYL TCP, day oily society manufacturing); Tert-butyl hydroperoxide pivalate (trade name: PERBUTYL PV; Day oily society manufacturing), uncle's hexyl peroxidating pivalate (trade name: PERHEXYL PV, day oily society manufacturing), tert-butyl hydroperoxide neodecanoic acid ester (trade name: PERBUTYLND, day oily society manufacturing), uncle's hexyl new decanoate ester peroxide (trade name: PERHEXYL ND; Day oily society manufacturing), uncle's hexyl peroxidating isopropyl monocarbonate (trade name: PERHEXYL I; Day oily society makes), 1-cyclohexyl-1-Methylethyl new decanoate ester peroxide (trade name: the fan of group! パ ー シ Network ロ) ND, a day oily society makes), 1,1; 3; 3-tetramethyl butyl new decanoate ester peroxide (trade name: PEROCTAND, a day oily society makes), cumyl new decanoate ester peroxide (trade name: PERCUMYL ND, day oily society manufacturing), (α; α '-two-Xin capryl peroxidating) diisopropyl benzene peroxyesters such as (trade name: for handkerchief (ダ イ パ ー) ND, a day oily society make) etc.
As azo is thermal polymerization, for example, can enumerate 2; 2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile) (the pure medicine manufactured of trade name: V-70 and light), 2; 2 '-azo two (2-cyclopropyl propionitrile) (the pure medicine manufactured of trade name: V-68 and light), 2,2 '-azo two (2; The 4-methyl pentane nitrile) azonitrile compound such as (the pure medicine manufactured of trade name: V-65 and light); 2; 2 '-azo two (2-methyl-N-phenyl third amidine) (trade name: VA-545; With the pure medicine manufactured of light), 2,2 '-azo two [N-(4-chlorphenyl)-2-methyl-prop amidine] dichloride hydrogen (the pure medicine manufactured of trade name: VA-546 and light), 2; 2 '-azo two [N-(4-hydroxy phenyl)-2-methyl-prop amidine] dichloride hydrogen (trade name: VA-548; With the pure medicine manufactured of light), 2,2 '-azo two [N-(4-aminophenyl)-2-methyl-prop amidine], four hydrogen chloride (the pure medicine manufactured of trade name: VA-500 and light), 2; 2 '-azo two [2-methyl-N-(phenyl methyl)-third amidine] dichloride hydrogen (trade name: VA-552; With the pure medicine manufactured of light), 2,2 '-azo two (2-methyl-N-propenyl third amidine) dichloride hydrogen (the pure medicine manufactured of trade name: VA-553 and light), 2; 2 '-azo two (2-methyl-prop amidine) dichloride hydrogen (trade name: VA-50; With the pure medicine manufactured of light), 2,2 '-azo two [N-(2-hydroxyethyl)-2-methyl-prop amidine] dichloride hydrogen azo amidine compounds such as (the pure medicine manufactured of trade name: VA-558 and light); 2,2 '-azo two [2-(5-methyl-2-imidazoline-2-yl) propane] dichloride hydrogen (the pure medicine manufactured of trade name: V-041 and light), 2; 2 '-azo two [2-(2-imidazoline-2-yl) propane] dichloride hydrogen (the pure medicine manufactured of trade name: V-044 and light), 2, [2-(4 for 2 '-azo two; 5,6,7-tetrahydrochysene-1H-1; 3-diaza
Figure BDA00002207123100141
-2-yl) propane] dichloride hydrogen (the pure medicine manufactured of trade name: V-054 and light), 2, [2-(3 for 2 '-azo two; 4,5,6-tetrahydropyrimidine-2-yl) propane] dichloride hydrogen (trade name: V-058; With the pure medicine manufactured of light), 2; 2 '-azo two [2-(5-hydroxyl-3,4,5; 6-tetrahydropyrimidine-2-yl) propane] dichloride hydrogen ring-type amidine compounds such as (the pure medicine manufactured of trade name: V-059 and light) etc.
Aforementioned radical polymerization initiator can use separately, also can be with also using more than 2 kinds.In addition, the cooperation ratio of this radical polymerization initiator is not special to be limited, but with respect to solidification compound 100 mass parts, preferably is limited to 0.1 mass parts down, is limited to 20 mass parts on preferably.If less than 0.1 mass parts, then the curable of sealant of the present invention may be not enough, and if surpass 10 mass parts, then unreacted radical polymerization initiator left behind in a large number, may stripping in liquid crystal.Be limited to 0.3 mass parts under preferred, be limited to 10 mass parts on preferred.
In addition, and when being with radically curing system and cationic curing, also can use to have the two compound of free-radical polymerised group and cationically polymerizable group.As having the two compound of free-radical polymerised group and cationically polymerizable group; For example, a part of epoxy radicals that can enumerate commercially available BPF epoxy radicals semicrystalline propylene acid esters, BPA epoxy radicals semicrystalline propylene acid esters (trade name of DAICEL-CYTEC manufactured " UVa1561 "), makes the compound that has a plurality of epoxy radicals in a part makes the compound of its (methyl) acryloyl groupization with the reaction of (methyl) acrylic acid.
Wherein, the dilution effect of BPF epoxy radicals semicrystalline propylene acid esters, BPA epoxy radicals semicrystalline propylene acid esters is high, is more preferably.
In the present invention; When being and, during specifically as radically curing system's (methyl) acryloyl group with as the composition of the epoxy radicals coexistence of cationic curing system, owing to passing through rayed or thermal treatment with radically curing system material with cationic curing system; Make epoxy radicals carry out cationic polymerization; (methyl) acryloyl group carries out free radical polymerization and solidifies, and is adhered to substrate securely, and is therefore preferred.At this moment, in order to solidify and carry out polymerization more efficiently, preferably in this solidification compound and with making epoxy radicals carry out the cationic polymerization initiators of cationic polymerization and the radical polymerization initiator that makes (methyl) acryloyl group carry out free radical polymerization.
Cation-curable bonding agent of the present invention through also using the alkali solid material, can further reduce metal protection.
(alkali solid material)
The alkali solid material that uses among the present invention so long as have the solid chemical compound of the function of neutralization or seizure acid, just can use arbitrarily.Owing to the polyreaction of cationically polymerizable compound is that the acid that is produced by cationic polymerization initiators causes, therefore after polymerization is fully carried out, need to neutralize, catch unnecessary acid.Therefore alkali solid material among the present invention may hinder cationic polymerization owing to use with the state that is included in the bonding agent.Therefore, require the alkali solid material to be insoluble to the cationically polymerizable compound in fact.The alkali solid solubility of substances is below 0.02 mass parts with respect to cationically polymerizable compound 100 mass parts preferably.If the dissolubility of alkali solid material is high, the acid that then produces is directly by the alkali solid material capture, and the polymerization of cationically polymerizable compound is not carried out, so adhesive property can't be given full play to.
In addition, for the acid that prevents to produce leaks into the outside from bonding agent, the particle diameter of alkali solid material is preferably less.Because the size of particle has physical boundaries, therefore when the particle of used alkali solid material directly was UA primary particle, it was preferably 0.01～50 μ m, 0.01～5 μ m more preferably, and further be preferably 0.01～1 μ m.When the particles aggregate of used alkali solid material and when forming offspring, the size of offspring is preferably above-mentioned scope.In addition, when being used for the encapsulant of LCD as the alkali solid material, because the restriction at interval of 2 plate bases, it is preferably 0.01～2 μ m.
As the inorganic alkaline solid matter; Can enumerate various inorganic salts (carbonate, phosphate, carboxylate etc.), metal oxide, metal sulfide, metal nitride, basic clay mineral etc., and on these inorganic solid surfaces, carry out material of basic treatment etc.Specifically; As inorganic salts; Lime carbonate, barium carbonate, magnesium carbonate, strontium carbonate, sodium carbonate, sal tartari, cesium carbonate, soda mint, saleratus, calcium bicarbonate, magnesium bicarbonate, zinc carbonate, calcium phosphate, magnesium phosphate, sodium phosphate, potassium phosphate, barium phosphate, sodium citrate, potassium citrate, calcium citrate, magnesium citrate, magnesium oxalate, sodium oxalate, potassium oxalate, sodium tartrate, potassium tartrate can be enumerated,, beaded glass, aluminium oxide (activated alumina), zeolite, titanium dioxide, zinc paste, silica gel, tin oxide, zirconia, magnesium oxide, the calcium oxide of alkalescence can be enumerated as metal oxide; As metal sulfide; The zinc sulphide of alkalescence can be enumerated,, the titanium nitride of alkalescence can be enumerated as metal nitride; As clay mineral; The talcum of alkalescence can be enumerated,, the magnesium hydroxide of alkalescence etc. can be enumerated as metal hydroxides.
In addition; In the present invention; As the alkali glass pearl of alkali solid material, alkaline oxygenated titanium, alkaline oxygenated zinc, alkaline silica gel, alkaline oxygenated tin, alkaline zirconia, alkali nitride titanium, alkaline zinc sulphide etc., for example can use nitrogen compounds such as silane coupling agent with basic groups such as organic amino or hexamethyldisilazane that metal oxide, metal nitride, metal sulfide as precursor are handled and made it become alkalescence.But the present invention is not limited thereto.
As the organic basic solid matter; Can enumerate have basic functional group through making (for example, the heterocyclic radical of organic amino, nitrogen atom, weak acid strong alkali salt functional group etc.) the polymer class that monomer polymerization synthesized, with the compound that contains basic functional group coupling processing is carried out on the surface of organic polymer pearl and material and the pearl class that is coated with this polymeric beads gained with the aforementioned polymer class.The present invention is not limited thereto.The organic basic solid matter can also use commercially available organic basic solid matter except can synthesizing through the whole bag of tricks.Specifically, can the give an example EPOMIN (Japanese catalyst society make) of polyethyleneimine.
In the present invention; As the alkali solid material; Be preferably basic clay mineral such as talcum, perhaps, can regenerate through surface treatment from easy importing basic functional group; Have enough surface areas; Safe, obtain easily, viewpoint easy and simple to handle is considered; Be preferably lime carbonate, barium carbonate, magnesium carbonate, soda mint, saleratus, calcium bicarbonate, magnesium bicarbonate, beaded glass, aluminium oxide (activated alumina), zeolite, titanium dioxide, zinc paste, monox and have basic functional group (for example, the heterocyclic radical of organic amino, nitrogen atom, weak acid strong alkali salt functional group etc.) polymer class, with the compound that contains basic functional group coupling processing is carried out on the surface of organic polymer pearl and material and the pearl class that is coated with this polymeric beads gained with the aforementioned polymer class.Wherein, basic clay mineral such as preferably talc, imported the monox of basic functional group.
Because alkalescence that alkali solid had can hinder the curing reaction of cationically polymerizable compound, therefore compare weak base base more preferably, the little material of basic group density on the perhaps preferred alkaline solid surface with strong-base group.This is owing to hope after the acid that cationic polymerization initiators produced fully causes the curing reaction of cationically polymerizable compound, the residual acid that can gently neutralize of the base of alkali solid.
(other composition silane coupling agent)
In addition, in order to improve cementability, can also in cationic curing type liquid crystal sealing agent of the present invention, mix known habitual silane coupling agent.In this silane coupling agent, owing to have the silane coupling agent of polymerizable groups such as (methyl) acryloyl group or epoxy radicals, can obtain high adhesiveness with radically curing system or the copolymerization of cationic curing based compound, therefore preferred especially.
As silane coupling agent, for example, can enumerate 3-(methyl) acryloxy propyl trimethoxy silicane, 3-epoxy oxygen base propyl trimethoxy silicane etc. with polymerizable group.As this commercial goods with silane coupling agent of polymerizable group; For example, can enumerate trade name " KBM503 " that chemical company of SHIN-ETSU HANTOTAI makes, " KBE503 ", " KBM502 ", " KBE502 ", " KBM5102 ", " KBM5103 ", " KBM403 " etc.
And the use amount during with aforementioned silane coupling agent, with respect to whole solidification compound amounts, preferably use, and be preferably the scope of 1～5 quality % especially with the scope of 0.1～10 quality %.When the ratio of silane coupling agent during, can't obtain sufficient adhesive effect, and when surpassing 10 quality %, may cause to be separated less than 0.1 quality %.Be limited to 0.5 mass parts under preferred, be limited to 5 mass parts on preferred.
(other composition)
For purposes such as viscosity adjustment, storage stabilities, can also in cationic curing type liquid crystal sealing agent of the present invention, suitably add known habitual adjuvant, filling agent.
For example, in the present invention the dispersed minichromosome vector of load cationically polymerizable compound, can also the proper fit filling agent.In order to add filling agent through cementability and the linear expansivity etc. that cooperate stress dispersion effect that filling agent produced to improve sealant of the present invention.For example, can enumerate organic fillers such as inorganic fillers such as talcum, asbestos, monox, zeyssatite, smectite, bentonitic clay, lime carbonate, magnesium carbonate, aluminium oxide, smectite, zeyssatite, magnesium oxide, titanium dioxide, magnesium hydroxide, hydrate of aluminium, beaded glass, barium sulphate, gypsum, calcium silicate, talcum, beaded glass, sericite, atlapulgite, bentonitic clay, polyester micropartical, polyurethane particulate, polyvinyl particulate, acrylate copolymer particulate.
The cooperation ratio of above-mentioned filling agent is not special to be limited, and as the use level that comprises the dispersed minichromosome vector of the present invention, with respect to above-mentioned solidification compound 100 mass parts, it preferably is limited to 1 mass parts down, is limited to 100 mass parts on preferably.If less than 1 mass parts, then can not get adding the effect of filling agent basically, and if, then may reduce the operability such as illustrative of sealant of the present invention above 100 mass parts.Be limited to 5 mass parts under preferred, be limited to 50 mass parts on preferred.
(viscosity)
If cationic curing type liquid crystal sealing agent of the present invention uses E type viscosity meter at 25 ℃, 2sec -1The viscosity of being measured down is more than the 100Pas, then can be more preferably as through after state the technology of dripping and make the used liquid crystal sealing agent of liquid crystal display cells.If less than 100Pas, then when making liquid crystal display cells, can't remain on the shape of formed seal pattern on the transparency carrier, and the stripping of sealant composition causes liquid crystal pollution in liquid crystal through the technology of dripping.Be limited to 100Pas under preferred, be limited to 5000Pas on preferred.If surpass 5000Pas, then the illustrative of sealant of the present invention is not enough, is difficult to make liquid crystal display cells through the technology of dripping.As viscometric E type viscosity meter at this moment, not special the qualification for example, can be used " DV-III " of Brookfield manufactured etc.
(liquid crystal sealing agent)
Cationic curing type liquid crystal sealing agent of the present invention, the sealant when making liquid crystal panel except being used as, can also be as after in liquid crystal panel, injecting liquid crystal material, the sealant of sealing inlet.
Liquid crystal panel; For example; Coating smooth cationic curing type liquid crystal sealing agent of the present invention on arbitrary real estate of front with thin film transistor (TFT), pixel electrode, alignment films, color filter, electrode etc. or back substrate; Paste another piece substrate then, and, liquid crystal panel sealing of the present invention is solidified with Photocurable composition from the substrate surface side of this substrate or the side-irradiation light of this substrate.Then, in the liquid crystal cell of gained, inject liquid crystal, seal inlet with sealant then, thereby can make liquid crystal panel.
In addition; Liquid crystal panel can obtain through technology under the liquid crystal drop; That is, use successively smooth cation-curable liquid crystal sealing agent of the present invention 2 electroded transparency carriers one on form the operation of seal pattern, the whole face operation of coating of liquid crystalline droplet of dripping in aforementioned seal pattern frame; Overlapping another transparency carrier also carries out bonding operation through aforementioned seal pattern, and aforementioned seal pattern is carried out light-struck operation.
When smooth cationic curing type liquid crystal sealing agent of the present invention; Demonstrate and behind irradiation ultraviolet radiation, can not solidify immediately and temporarily keep the viscous fluid state; And after the what is called of solidifying when postponing curable, can also through use successively smooth cation-curable liquid crystal sealing agent of the present invention 2 electroded transparency carriers one on form the operation of seal pattern, aforementioned seal pattern carried out light-struck operation, in aforementioned seal pattern frame whole face drip the coating of liquid crystalline droplet operation and overlapping another transparency carrier and carry out bonding operation through aforementioned seal pattern and obtain.
As demonstrating the cationic curing type liquid crystal sealing agent that postpones curable, can enumerate aforementioned male photopolymerizable compound, and the composition of this compound and response delay agent.As this response delay agent, not special the qualification for example, can be used polyol compound etc.Through containing above-mentioned response delay agent, can control cationic curing type liquid crystal sealing agent irradiates light of the present invention or pot life and set time after heat-treating.In above-mentioned polyol compound; Special aliphatic polyvalent alcohol; And as this aliphatic polyol; For example, can enumerate the material that makes spent glycol, propylene glycol, polyglycol, polypropylene glycol, butylene glycol etc. (gathering) aklylene glycol, glycerine, polyglycerol, pentaerythrite, polycaprolactone polyol, crown ether etc.On the other hand, the kind of the light cationic polymerization initiators of dispersed minichromosome vector institute load is not special to be limited, and can use aforementioned substances.
In order on real estate, to form cationic curing type liquid crystal sealing agent of the present invention, preferably use point gum machine to be coated with, perhaps be coated with through silk screen print method.At this moment, coating is live width 0.08～2mm, high 5～50 μ m of line usually.
Be used to make the light of smooth cationic curing type liquid crystal sealing agent curing of the present invention, be preferably ultraviolet ray or visible light, the light of wherein preferred 300nm～400nm wavelength.As light source, for example, can use high-pressure mercury-vapor lamp, metal halide lamp etc.If this illumination intensity of light source is 500W/m 2More than, then solidify rapidly, therefore preferred.The light quantity of irradiation is 20000J/m if be scaled to the accumulation light quantity 2More than, then can be cured well.In addition; Smooth cationic curing type liquid crystal sealing agent of the present invention, even under air atmosphere, also demonstrate good photo-curable, and if under nonactive property atmospheres such as nitrogen, carry out photocuring; Then can be cured, therefore be more preferably with less accumulation light quantity.
Embodiment
Below, specify the present invention through embodiment and comparative example.In addition, the evaluation for cementability, voltage retention is described below.
(making the manufacturing approach that example 1 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
The ADEKAOPTOMER SP150 that uses Asahi Denka Co., Ltd. is as the light cationic polymerization initiators.In addition, SP150 is that solid component concentration is 50% carbonic allyl ester (プ ロ ピ オ ン カ ー ボ ネ ー ト) solution, after the use amount (mass parts) stated be the mass parts that comprises solvent.
In the acetone of 20 mass parts, add and dissolve the light cationic polymerization initiators " SP150 " of 1 mass parts.Then, " the Aerosil300 surface area is 300m to the monox that adding 1 mass parts Japan Aerosil Co., Ltd. makes in the acetone soln of this " SP150 " 2/ g ", and through ultrasonic dispersing machine it is dispersed in the solution.Then, down with this dispersion soln vacuum drying and heat up in a steamer acetone, obtain loading on light cationic polymerization initiators (A) on the dispersed minichromosome vector (below be called load light cationic polymerization initiators (A)) in room temperature (20～25 ℃).On calculating, the light cationic polymerization initiators is 0.5g (owing to be NV.50 quality %, therefore being essentially 0.5 mass parts)/(1g * 300m with respect to the charge capacity of monox 2/ g)=1.7 * 10 -3G/m 2Use fluorescent x-ray analyzer to obtain the characteristic X-ray strength ratio of monox and sulphur; And infer the content of light cationic polymerization initiators by the content of sulphur; Calculate containing of this initiating agent proportional (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators), the result is 28 quality %.Therefore, the light cationic polymerization initiators that is calculated by the fluorescent x-ray analyzer value of obtaining is 1.3 * 10 with respect to the charge capacity of monox -3G/m 2
(making the manufacturing approach that example 2 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
In the formed mixed solvent of water of the acetone of 16 mass parts and 4 mass parts, add and dissolve the light cationic polymerization initiators " S P150 " of 1 mass parts.Then, " the Aerosil300 specific surface area is 300m to the monox that adding 1 mass parts Japan Aerosil Co., Ltd. makes in the solution of this " SP150 " 2/ g ", and through ultrasonic dispersing machine it is dispersed in the solution.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, directly at room temperature proceed vacuum drying again.After heating up in a steamer acetone, under the state that water freezes, directly carry out vacuum drying, promptly so-called freeze drying.In order from dried this silica supported smooth cationic polymerization initiators, to remove the initiating agent that is adsorbed on outside the pore, carry out following washing.This silica supported smooth cationic polymerization initiators of 20 mass parts is dispersed in the ethyl acetate solution of 100 mass parts, stirs, and remove ethyl acetate with centrifugal separator.Repeat to amount to 4 such operations, then this silica supported smooth cationic polymerization initiators after the centrifuging is stirred in the ultrapure water of 100 mass parts, and remove with centrifugal separator and to anhydrate.Repeat to amount to 4 such operations, with this silica supported smooth cationic polymerization initiators vacuum drying at room temperature after the centrifuging, obtain load light cationic polymerization initiators (B) again.
Use fluorescent x-ray analyzer; It is proportional to obtain containing of light cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators) is 12 quality %.Therefore, containing the proportional light cationic polymerization initiators that calculates by this is 4.5 * 10 with respect to the charge capacity of monox -4G/m 2
(making the manufacturing approach that example 3 loads on the hot cationic polymerization initiators on the dispersed minichromosome vector)
In the formed mixed solvent of water of the acetone of 16 mass parts and 4 mass parts, add and dissolve the hot cationic polymerization initiators " San-Aid SI100L " of 1 mass parts.Then, " the Aerosil300 specific surface area is 300m to the monox that adding 1 mass parts Japan Aerosil Co., Ltd. makes in the solution of this " SI100L " 2/ g ", and through ultrasonic dispersing machine it is dispersed in the solution.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, directly at room temperature proceed vacuum drying again.After heating up in a steamer acetone, under the state that water freezes, directly carry out vacuum drying, promptly so-called freeze drying.In order from dried this silica supported hot cationic polymerization initiators, to remove the initiating agent that is adsorbed on outside the pore, carry out following washing.This silica supported hot cationic polymerization initiators of 20 mass parts is dispersed in the ethyl acetate solution of 100 mass parts, stirs, and remove ethyl acetate with centrifugal separator.Repeat to amount to 4 such operations, then this silica supported hot cationic polymerization initiators after the centrifuging is stirred in the ultrapure water of 100 mass parts, and remove with centrifugal separator and to anhydrate.Repeat to amount to 4 such operations, with this silica supported hot cationic polymerization initiators vacuum drying at room temperature after the centrifuging, obtain the hot cationic polymerization initiators of load (C) again.
Use fluorescent x-ray analyzer; It is proportional to obtain containing of hot cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of hot cationic polymerization initiators)/(load quality of monox+hot cationic polymerization initiators) is 9 quality %.Therefore, containing the proportional hot cationic polymerization initiators that calculates by this is 3.3 * 10 with respect to the charge capacity of monox -4G/m 2
(making the manufacturing approach that example 4 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
At first prepare MCM41 as monox mesopore porous body.To join in the ion exchange water of 60 mass parts as 7.3 mass parts surfactants, the INCROQUAT TMC-80 (C22TMACl) of template; Dissolving fully under 60 ℃; Add the aqueous sulfuric acid of 24 mass parts 10% (w/w) then, form a liquid.Water glass (SiO to 10 mass parts 2, 36-38%, Na 2O, 17-19%) the middle 20ml ion exchange water that adds forms b liquid.A liquid is remained on 60～65 ℃, on one side vigorous stirring with the sulfuric acid of 10% (w/w) pH of reactant liquor is adjusted to 8.5 on one side to wherein adding b liquid, then stirred 5～8 hours.Then, this mixed liquor is transferred in the autoclave of 250ml, 105 ℃ of thermal treatments of carrying out 2 days～5 days.The vacuum filtration reactant liquor obtains about 9g crude product.45 ℃ of air dried 24 hours, and calcining 6 hours in 550 ℃ electric furnace obtained the mesopore porous body (c) that about 4.5g has removed template with crude product.Measure the fine pore and the surface area of mesopore porous body with N2 adsorbent equipment (Autosorb).Fine pore is 4.6nm, and specific surface area is 1080m 2/ g.
In the formed mixed solvent of water of the acetone of 16 mass parts and 4 mass parts, add and dissolve the light cationic polymerization initiators " SP150 " of 1 mass parts.Then, in the solution of this " SP150 ", add the above-mentioned mesopore porous body (c) of 1 mass parts, and it is dispersed in the solution through ultrasonic dispersing machine.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, proceed vacuum drying again.After heating up in a steamer acetone, under the state that water freezes, directly carry out vacuum drying, promptly so-called freeze drying.In order from dried silica supported smooth cationic polymerization initiators, to remove the initiating agent that is adsorbed on outside the pore, carry out following washing.This silica supported smooth cationic polymerization initiators of 20 mass parts is dispersed in the ethyl acetate solution of 100 mass parts, stirs, and remove ethyl acetate with centrifugal separator.Repeat to amount to 4 such operations, then the silica supported smooth cationic polymerization initiators after the centrifuging is stirred in the ultrapure water of 100 mass parts, and remove with centrifugal separator and to anhydrate.Repeat to amount to 4 such operations, with this silica supported smooth cationic polymerization initiators vacuum drying at room temperature after the centrifuging, obtain load light cationic polymerization initiators (D) again.
Use fluorescent x-ray analyzer; It is proportional to obtain containing of light cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators) is 18 quality %.Therefore, containing the proportional light cationic polymerization initiators that calculates by this is 2.0 * 10 with respect to the charge capacity of monox -4G/m 2
(making the manufacturing approach that example 5 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
In the formed mixed solvent of water of the acetone of 16 mass parts and 4 mass parts, add and dissolve the light cationic polymerization initiators " SP150 " of 2 mass parts.Then, in the solution of this " SP150 ", add the monox " Aerosil300 " that 1 mass parts Japan Aerosil Co., Ltd. makes, and it is dispersed in the solution through ultrasonic dispersing machine.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, directly at room temperature proceed vacuum drying and freeze drying again.With it as load light cationic polymerization initiators (E).
Use fluorescent x-ray analyzer; It is proportional to obtain containing of light cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators) is 62 quality %.Therefore, containing the proportional light cationic polymerization initiators that calculates by this is 5.4 * 10 with respect to the charge capacity of monox -3G/m 2
(making the manufacturing approach that example 6 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
In the formed mixed solvent of water of the acetone of 16 mass parts and 4 mass parts, add and dissolve the light cationic polymerization initiators " SP150 " of 0.2 mass parts.Then, in the solution of this " SP150 ", add 1 mass parts and make the MCM41 described in the example 4, and it is dispersed in the solution through ultrasonic dispersing machine.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, directly proceed vacuum drying and freeze drying again.With it as load light cationic polymerization initiators (F).
Use fluorescent x-ray analyzer; It is proportional to obtain containing of light cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators) is 4 quality %.Therefore, containing the proportional light cationic polymerization initiators that calculates by this is 3.9 * 10 with respect to the charge capacity of monox -5G/m 2
(making the manufacturing approach that example 7 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
In the formed mixed solvent of water of the acetone of 16 mass parts and 4 mass parts, add and dissolve the light cationic polymerization initiators " SP150 " of 1 mass parts.Then, " (specific surface area is 50m to Aerosil OX50 to the monox that adding 1 mass parts Japan Aerosil Co., Ltd. makes in the solution of this " SP150 " 2/ g) ", and through ultrasonic dispersing machine it is dispersed in the solution.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, directly proceed vacuum drying and freeze drying again.In order from dried load light cationic polymerization initiators, to remove the initiating agent that is adsorbed on outside the pore, carry out following washing.This silica supported smooth cationic polymerization initiators of 20 mass parts is dispersed in the ethyl acetate solution of 100 mass parts, stirs, and remove ethyl acetate with centrifugal separator.Repeat to amount to 4 such operations, then the silica supported smooth cationic polymerization initiators after the centrifuging is stirred in the ultrapure water of 100 mass parts, and remove with centrifugal separator and to anhydrate.Repeat to amount to 4 such operations, with the load light cationic polymerization initiators vacuum drying at room temperature after the centrifuging, obtain load light cationic polymerization initiators (G) again.
Use fluorescent x-ray analyzer; It is proportional to obtain containing of light cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators) is 2 quality %.Therefore, containing the proportional light cationic polymerization initiators that calculates by this is 4.1 * 10 with respect to the charge capacity of monox -4G/m 2
(making the manufacturing approach that example 8 loads on the light cationic polymerization initiators on the dispersed minichromosome vector)
In the formed mixed solvent of water of the acetone of 64 mass parts and 16 mass parts, add and dissolve the light cationic polymerization initiators " SP150 " of 0.02 mass parts.Then, in the solution of this " SP150 ", add 5 mass parts and make the MCM41 described in the example 4, and it is dispersed in the solution through ultrasonic dispersing machine.This dispersion soln is remained on below 0 ℃, and directly carry out vacuum drying, heat up in a steamer acetone, directly proceed vacuum drying and freeze drying again.With it as load light cationic polymerization initiators (H).
Use fluorescent x-ray analyzer; It is proportional to obtain containing of light cationic polymerization initiators by the characteristic X-ray strength ratio of monox and sulphur, and (load quality of light cationic polymerization initiators)/(load quality of monox+light cationic polymerization initiators) is 0.1 quality %.Therefore, containing the proportional light cationic polymerization initiators that calculates by this is 9.3 * 10 with respect to the charge capacity of monox -7G/m 2
(embodiment 1)
The load light cationic polymerization initiators (A) of 2 mass parts is added in the epoxy monomer " EXA850crp " that Dainippon Ink Chemicals of 22 mass parts makes, and use rotation revolution formula mixer THINKYAR250 to mix, form sealant (A).
At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 2.5 mass parts, and dispersed minichromosome vector is 6.5 mass parts.
(mensuration of evaluation method voltage retention)
1 mass parts sealant (A) is joined in the liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals of 20 mass parts makes, preserved 1 hour at 120 ℃.At room temperature with its taking-up and leave standstill, liquid crystal and sealant (A) are separated.Take lcd segment, measure voltage retention as supernatant.Voltage retention; Be that to prepare GAP between the glass substrate of 2 band ITO electrodes be 5 microns liquid crystal cell; At 23 ℃ the liquid crystal cell that has injected aforementioned supernatant liquid crystal is applied the initial stage voltage that 64 microseconds exchange 5V; Obtain the voltage ratio of 200 milliseconds and 2000 milliseconds frame time front and back, it multiply by 100 as voltage retention.
The result is shown in table 1.
(comparative example 1)
The light cationic polymerization initiators " SP150 " of 1 mass parts is mixed with the epoxy monomer " EXA850crp " of 22 mass parts, then, form sealant (H1) to wherein adding 1 mass parts monox " Aerosil300 " and mixing.
According to aforementioned evaluation method, measure voltage retention.The result is shown in table 1.
(comparative example 2)
The light cationic polymerization initiators " SP150 " of 1 mass parts is mixed with the epoxy monomer " EXA850crp " of 22 mass parts, form sealant (H2).
According to aforementioned evaluation method, measure voltage retention.The result is shown in table 1.
(reference example 1)
The epoxy monomer " EXA850crp " of 1 mass parts is joined in the liquid crystal " PA-0211CA033 " of 20 mass parts, preserved 1 hour at 120 ℃.At room temperature with its taking-up and leave standstill, liquid crystal and epoxy monomer produce and are separated, and take the lcd segment of supernatant.Measure the voltage retention of the liquid crystal of taking.The result is shown in table 1.
(reference example 2)
Only measure the voltage retention of liquid crystal " PA-0211CA033 ".The result is shown in table 1.
As shown in table 1, use the liquid crystal of the embodiment 1 of sealant (A), demonstrated with reference example 2 in be merely liquid crystal phase with voltage retention.But; Do not load on the monox and light cationic polymerization initiators and monox join comparative example 1 in the epoxy monomer respectively, only added the comparative example 2 of light cationic polymerization initiators; Its voltage retention is lower than reference example 2, and this has hinted that the stripping of light cationic polymerization initiators is in liquid crystal.
In addition, only add the voltage retention of the reference example 1 of epoxy monomer, also be lower than the voltage retention that is merely liquid crystal in the reference example 2.Therefore, it has hinted that epoxy monomer itself also has the factor that reduces voltage retention.Yet; Voltage retention shown in the application embodiment 1; Higher than the voltage retention of reference example 1, so it has hinted that (embodiment's 1) of the present invention loads on light cationic polymerization initiators on the dispersed minichromosome vector and can adsorb in the monomer existing impurity etc.
[table 1]
Figure BDA00002207123100261
(embodiment 2)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the load light cationic polymerization initiators (B) of 9 mass parts, and use three-roller mixing, form sealant (B).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 1.1 mass parts, and dispersed minichromosome vector is 7.9 mass parts.
5% alcohol dispersion liquid of the sept " LH11S " that Chuan Xiangjiaoshe makes is sprayed on the glass substrate that has ITO " RZ-B107N1N " of 1 EHC society manufacturing with morning.Then, having at another sheet through point gum machine on the glass substrate of ITO and be coated with sealant (B), is about 1mm thereby make the sealant width of the liquid crystal panel of final gained.Coating sealant (B), it is inboard making electrode, and forms the rectangle delineation lines of surrounding this electrode.Then, use high-voltage metal-halide lamp, to sealing agent (B) part shine 20 second 500W/m 2Ultraviolet ray.Before the curing reaction of sealant (B) finishes; To sealant (B) inboard of the rectangle liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals of appropriate amount makes that drips; And it is bonding that its glass substrate with the sept of having sprayed is carried out to ground relatively, makes liquid crystal panel.Is after 60 ℃, humidity are to keep 480 hours in 90% the constant temperature and humidity cabinet, to measure voltage retention with this liquid crystal panel in temperature.Voltage retention is under 23 ℃, to apply the initial stage voltage that 64 microseconds exchange 5V, obtains the voltage ratio before and after 167 milliseconds of frame times, and it multiply by 100 obtains.The result is shown in table 2.
(embodiment 3)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the hot cationic polymerization initiators of load (C) of 9 mass parts, and use three-roller mixing, form sealant (C).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 0.8 mass parts, and dispersed minichromosome vector is 8.2 mass parts.
5% alcohol dispersion liquid of the sept " LH11S " that Chuan Xiangjiaoshe makes is sprayed on the glass substrate that has ITO " RZ-B107N1N " of 1 EHC society manufacturing with morning.Then, having at another sheet through point gum machine on the glass substrate of ITO and be coated with sealant (C), is about 1mm thereby make sealant (C) width of the liquid crystal panel of final gained.Coating sealant (C), it is inboard making electrode, and forms the rectangle delineation lines of surrounding this electrode.With it 120 ℃ of 60 seconds of thermal treatment.Before the curing reaction of sealant (C) finishes; To sealant (C) inboard of the rectangle liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals of appropriate amount makes that drips; And it is bonding that its glass substrate with the sept of having sprayed is carried out to ground relatively, makes liquid crystal panel.This panel was handled 1 hour at 120 ℃, promoted the curing of sealant (C).
Likewise measure voltage retention with embodiment 2, the result is shown in table 2.
(embodiment 4)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the load light cationic polymerization initiators (D) of 9 mass parts, and use three-roller mixing, form sealant (D).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 1.6 mass parts, and dispersed minichromosome vector is 7.4 mass parts.
Likewise measure voltage retention with embodiment 2, the result is shown in table 2.
(embodiment 5)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the load light cationic polymerization initiators (E) of 9 mass parts, and use three-roller mixing, form sealant (E).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 5.6 mass parts, and dispersed minichromosome vector is 3.4 mass parts.
Likewise measure voltage retention with embodiment 2, the result is shown in table 2.
(embodiment 6)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the load light cationic polymerization initiators (F) of 9 mass parts, and use three-roller mixing, form sealant (F).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 0.4 mass parts, and dispersed minichromosome vector is 8.6 mass parts.
Likewise measure voltage retention with embodiment 2, the result is shown in table 2.
(embodiment 7)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the load light cationic polymerization initiators (G) of 9 mass parts, and use three-roller mixing, form sealant (G).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 0.2 mass parts, and dispersed minichromosome vector is 8.8 mass parts.
Likewise measure voltage retention with embodiment 2, the result is shown in table 2.
(embodiment 8)
Add 1 of the epoxy monomer " EXA850crp " of 70 parts of Dainippon Ink Chemicals' manufacturings, 30 parts of long rapids NagaseChemtex manufactured of Japan; 6-hexanediol diglycidyl ether " DENACOL EX-212-L ", 5 parts of silane series coupling agents " KBM403 " that Shin-Etsu Chemial Co., Ltd makes, and use rotation revolution formula mixer THINKY AR250 to be mixed to evenly.Then, add the load light cationic polymerization initiators (H) of 9 mass parts, and use three-roller mixing, form sealant (H).At this moment, with respect to cationically polymerizable compound 100 mass parts, cationic polymerization initiators is 0.01 mass parts, and minichromosome vector is 8.8 mass parts.
Likewise measure voltage retention with embodiment 2, the result is shown in table 2.
[table 2]
Figure BDA00002207123100291
(embodiment 9)
The load light cationic polymerization initiators (A) of interpolation 2 mass parts in the Mitsubishi chemical Co., Ltd " PTMG1000 " of " EPIKOTE 807 " of epoxy monomer " EPIKOTE 828 " that japan epoxy resin Co., Ltd. of 10 mass parts makes, 10 mass parts, 2.5 mass parts; And use rotation revolution formula mixer THINKYAR250 to mix, form sealant (I).
Prepare the glass substrate RS-B107M1N (have the alignment films of grinding, have ITO) that 2 EHC societies make, and on a slice wherein 5% alcohol dispersion liquid of the sept " LH11S " of spraying Chuan Xiangjiaoshe morning manufacturing.Then, using point gum machine on another sheet glass substrate is that the rectangle of about 1mm is coated with above-mentioned sealant (I) in the outer edge of substrate with the sealed width.Then, use high-voltage metal-halide lamp, to the sealing agent partly shine 40 second 500W/m 2Ultraviolet ray.Then, under vacuum on the rectangle on this substrate the sealant inboard liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals of appropriate amount makes that drips, it is bonding that the grinding direction quadrature of 2 sheet glass substrates is carried out, and makes liquid crystal cell.This liquid crystal cell is back in the atmosphere, and substrate distance is the size of sept, and it was placed 1 hour, postpones to solidify until sealant (I), makes the liquid crystal panel of TN type.
Make optic axis overlap ground with this liquid crystal panel double team between the Polarizer of 2 quadratures, make liquid crystal display cells.It has demonstrated good show state, is the bright demonstration that seems transparent under the state that does not apply voltage promptly, is that lighttight the showing slinkingly of electrode part of liquid crystal cell shown when applying voltage.
(comparative example 3)
The light cationic polymerization initiators " SP150 " of interpolation 1 mass parts in the Mitsubishi chemical Co., Ltd " PTMG1000 " of " EPIKOTE 807 " of epoxy monomer " EPIKOTE 828 " that japan epoxy resin Co., Ltd. of 10 mass parts makes, 10 mass parts, 2.5 mass parts; And use rotation revolution formula mixer THINKYAR250 to mix, form sealant (H3).
Except sealant (B) is changed to the sealant (H3), other condition is identical with embodiment 2, makes liquid crystal cell.That is, prepare the glass substrate RS-B107M1N (have the alignment films of grinding, have ITO) that 2 EHC societies make, and on a slice wherein 5% alcohol dispersion liquid of the sept " LH11S " of spraying Chuan Xiangjiaoshe morning manufacturing.Then, using point gum machine on another sheet glass substrate is that the rectangle of about 1mm is coated with aforementioned sealant (H3) in the outer edge of substrate with the sealed width.Then, use high-voltage metal-halide lamp, to the sealing agent partly shine 40 second 500W/m 2Ultraviolet ray.Then, under vacuum on the rectangle on this substrate the inboard of sealant (H3) liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals of appropriate amount makes that drips, it is bonding that the grinding direction quadrature of 2 sheet glass substrates is carried out, and makes liquid crystal cell.This liquid crystal cell is back in the atmosphere, and is compressed to the size that substrate distance is a sept, then it was placed 1 hour, postpone to solidify, make the liquid crystal panel of TN type until sealant (H3).
Same with embodiment 9, make optic axis overlap ground with this liquid crystal panel double team between the Polarizer of 2 quadratures, make liquid crystal display cells.Yet different with embodiment 2, its periphery at sealant under the state that does not apply voltage has shown opaque part, and the part of electrode part shows slinkingly and shows and show as grey when applying voltage.
Comparison through embodiment 9 and comparative example 3 demonstrates the sealant that uses the inventive method made, and its liquid crystal pollution property is little.Can think that this is owing to thereby the amount of from sealant, leaking the light cationic polymerization initiators that can pollute liquid crystal is less.
(stripping again of reference experiment load light cationic polymerization initiators)
In 24 parts of acetone, add 1 part of load light cationic polymerization initiators (A) of making gained in the example 1; And in sonic washing machine, vibrated 30 minutes; Make solution (B); Measure the amount of the light cationic polymerization initiators of stripping again in this solution (B), with it as " the polymerization initiator amount of stripping ".Not stripping and remaining light cationic polymerization initiators amount is evaluated as with enough strong adhesion and loads on the polymerization initiator amount on the silicon dioxide.The result is shown in table 3.
With above-mentioned identical condition under, the charge capacity of the dispersed minichromosome vector that appropriate change uses and the light cationic polymerization initiators of load is made other load light cationic polymerization initiators.Likewise measure " the polymerization initiator amount of stripping ".The result is shown in table 3.
The quality of the light cationic polymerization initiators that uses in " total polymerization amount of initiator " expression load light cationic polymerization initiators (A) in the table 3 and other the light cationic polymerization initiators.Therefore, (the polymerization initiator amount of stripping)/(total polymerization amount of initiator) representes that stripping again is the mass ratio of the light cationic polymerization initiators in the acetone to solution (B).
This result shows the kind regardless of the dispersed minichromosome vector that uses; And charge capacity regardless of the light cationic polymerization initiators of load; All stripping is in the solution (B) again for 30～60% light cationic polymerization initiators, so it has hinted that 70～40% light cationic polymerization initiators is with enough strong adhesion and silica bound.
[table 3]
Figure BDA00002207123100311
(making the adjustment of routine 9 alkali solid materials (1))
Alkali solid material (1) imports basic functional group and makes on the surface of aerosil.As aerosil, the R976S that uses Japanese Aerosil (strain) to make.Below manufacturing conditions is described.The mass ratio that each embodiment forms is summarized in table-1.
To be dissolved in by in 1800 mass parts ethanol and the formed solution of 200 mass parts water as the γ-An Jibingjisanyiyangjiguiwan (LS3150, SHIN-ETSU HANTOTAI's chemical industry (strain)) of silane coupling agent.Meltage is shown in table-1.
The R976S that 100 mass parts aerosils (Aerosil (strain)) are made is immersed in this solution, and mixes 10 minutes with the ultrasonic dispersing device.This solution being heated on 150 ℃ the hot plate heat treated 1.5 hours, is obtained powder.
For remove unreacted reactant with or not with the polymkeric substance of the silane coupling agent of aerosil surface combination; This powder of 100 mass parts is dispersed in the 2000 mass parts ethanol; And, carry out centrifuging then with ultrasonic treatment unit vibration 10 minutes, obtain powder.Repeat 2 these washings again.This powder at 80 ℃ of heated-air drying 4hr, is formed alkali solid material (1).
[table 4]
Figure BDA00002207123100321
(embodiment 10)
Use the sealant (D) described in the 100 mass parts embodiment 4, and use rotation revolution formula mixer THINKY AR250 that it is mixed with 2.5 mass parts alkali solid materials (1), obtain sealant (J).
(embodiment 11)
Use the sealant (D) described in the 100 mass parts embodiment 4; And use the rotation revolution formula mixer THINKY AR250 talcum " Micoud is reined in (ミ Network ロ ラ イ ト) (manufacturing of the former chemical industry of bamboo (strain) society) " that it is commercially available with 20 mass parts to mix, obtain sealant (K).
(evaluation Example is extracted the pH of water)
Be described below, the pH of the extraction water that carries out from bonding agent, extracting measures.After to the bonding agent irradiation ultraviolet radiation, in order quantitatively to be exuded to the acid that outside light acid producing agent is generated, will shine ultraviolet bonding agent and be impregnated in the ultrapure water from bonding agent, measure its pH.In order to carry out this mensuration, it is 4.2cm that the above-mentioned bonding agent of 0.5g is joined floorage 2The glass container in, take off the lid of glass container, irradiation 500W/m from the top 2The ultraviolet 20000J/m of intensity 2In this glass container, inject the ultrapure water of 5g then immediately, add a cover, in remaining 80 ℃ calibration cell, left standstill 1 hour, be cooled to room temperature (23 ℃) then, measure pH.The result is shown in table 5.
[table 5]
Table 5 The sealant name Alkali solid material name Addition Extract the pH of water
Embodiment 10 Sealant (J) （1） 2.5 mass parts 7.1
Embodiment 11 Sealant (K) Micoud is reined in 20 mass parts 7.1
It is more than 5 that this result demonstrates the pH that extracts water, and its expression alkali solid material neutralizes or caught the acid that the light acid producing agent is generated.
(the promotion test of evaluation Example electrode corrosion)
To the sealant (J) of embodiment 10,11 and (K) carry out the promotion test of electrode corrosion.
Be coated on the liquid crystal cell that has broach shape electrode with aforementioned sealant (J) with (K) with spreader, making thickness is 10 μ m, and irradiation ultraviolet radiation (intensity is 50mW/cm 2) 40 seconds, make its curing.
(broach shape electrode is formed by chromium, and electrode is wide to be 10 μ m)
Broach shape electrode is divided into 2 systems and contends with, and combines with the mutually nested mode of broach each other, and electrode gap each other is 10 μ m.On one side to applying the DC voltage of 10V between electrode; Under 60 ℃-90% environment, kept 3 days on one side; Promote electrode corrosion, use the observation by light microscope electrode then, and will not produce be evaluated as " ◎ " of electrode corrosion; Be evaluated as " zero " who produces electrode corrosion slightly, be evaluated as " * " that produces electrode corrosion.The result is shown in table 6.
[table 6]
Table 6 The sealant name Alkali solid material name Addition The generation of electrode corrosion
Embodiment 10 Sealant (J) （1） 2.5 mass parts ◎
Embodiment 11 Sealant (K) Micoud is reined in 20 mass parts ◎
The result uses sealant (J) and material (K), does not produce electrode corrosion fully.This result demonstrates the neutralization of alkali solid material or has caught the acid that the light acid producing agent is generated.
(embodiment 12 making of liquid crystal panel of technology (employing drip))
Prepare the glass substrate RS-B107M1N (have the alignment films of grinding, have ITO) that 2 EHC societies make, and to wherein one go up the sept " LH11S " of spraying Chuan Xiangjiaoshe morning manufacturing 5% alcohol dispersion liquid.Then, the sealant (J) that uses point gum machine in the outer edge of substrate coating embodiment 10, to make, and use high-voltage metal-halide lamp at the rectangle that on another sheet glass substrate is about 1mm with the sealed width, to the sealing agent partly shine 40 second 500W/m 2Ultraviolet ray.Then, the inboard of the rectangular seal agent under vacuum on this substrate liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals of appropriate amount makes that drips, it is bonding that the grinding direction quadrature of 2 sheet glass substrates is carried out, and makes liquid crystal cell.This liquid crystal cell is back in the atmosphere, makes the liquid crystal panel of TN type.
Make optic axis overlap ground with this liquid crystal panel double team between the Polarizer of 2 quadratures, make liquid crystal display cells.It has demonstrated good show state, is the bright demonstration that seems transparent under the state that does not apply voltage promptly, is that lighttight the showing slinkingly of electrode part of liquid crystal cell shown when applying voltage.
< voltage retention test >
5% alcohol dispersion liquid of the sept " LH11S " that Chuan Xiangjiaoshe makes is sprayed on the glass substrate that has ITO " RZ-B107N1N " of 1 EHC society manufacturing with morning.Then; Use point gum machine to have at another sheet to be coated with on the glass substrate of ITO the sealant (J) of embodiment 10,11 or (K) with the width of about 1mm; Thereby two place's liquid crystal injecting ports are set in the outer edge of substrate, then 2 sheet glass substrates are carried out to ground relatively bonding, and under nitrogen atmosphere; Use high-voltage metal-halide lamp, to the sealing agent partly shine 40 second 500W/m 2Ultraviolet ray, make the liquid crystal cell in 2 holes.Under vacuum, in the liquid crystal cell in 2 holes, inject the liquid crystal " PA-0211CA033 " that Dainippon Ink Chemicals makes; Directly not contacting ultraviolet form with aforementioned liquid-crystal compsn covers; With sealant (J) or (K) sealing 2 holes; And under nitrogen atmosphere, use high-voltage metal-halide lamp, shine once more 40 second 500W/m 2Ultraviolet ray, make liquid crystal panel.
The liquid crystal panel that preceding method is made carries out 60 ℃, 90% RH damp heat exposure test, measures the voltage retention after 120 hours.Voltage retention is under 24 ℃, liquid crystal panel to be applied the initial stage voltage that 64 microseconds exchange 5V, obtains the voltage ratio before and after 167 milliseconds of frame times, and it multiply by 100 obtains.
[table 7]
Table 7 The sealant name Alkali solid material name Addition Voltage retention (%)
Embodiment 10 Sealant (J) （1） 2.5 mass parts 98
Embodiment 11 Sealant (K) Micoud is reined in 20 mass parts 98

Claims (6)

1. a cationic curing type liquid crystal sealing agent is characterized in that, contains the cationically polymerizable compound and loads on light cationic polymerization initiators and/or the hot cationic polymerization initiators on the dispersed minichromosome vector.
2. cationic curing type liquid crystal sealing agent as claimed in claim 1; Wherein, With respect to aforementioned male photopolymerizable compound, contain aforementioned light cationic polymerization initiators and/or the hot cationic polymerization initiators that loads on the dispersed minichromosome vector of 1～30 quality %.
3. according to claim 1 or claim 2 cationic curing type liquid crystal sealing agent, wherein, the surface area of aforementioned dispersed minichromosome vector is 1～5000m 2The scope of/g.
4. like each described cationic curing type liquid crystal sealing agent of claim 1～3, wherein, aforementioned lights cationic polymerization initiators and/or hot cationic polymerization initiators are 1 * 10 with respect to the charge capacity of aforementioned dispersed minichromosome vector -6G/m 2～1g/m 2Scope.
5. like each described cationic curing type liquid crystal sealing agent of claim 1～4, it contains the alkali solid material.
6. liquid crystal display cells; It is characterized in that; Have against each other to two substrates, be arranged on the sealant between aforesaid base plate and be sealing into the liquid crystal in the sealing area that aforementioned encapsulant surrounds, and it uses each described cationic curing type liquid crystal sealing agent of claim 1～5 as aforementioned sealant.
CN201080065897.6A 2010-12-13 2010-12-13 Cationic curing type liquid crystal sealing agent and liquid crystal display cells Expired - Fee Related CN102822731B (en)

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